1. Field of the Invention
This invention relates to high-internal-phase emulsions. High internal-phase emulsions, hereafter referred to as HIPE'S, are liquid/liquid immiscible dispersed systems wherein the volume of the internal or dispersed phase occupies a volume more than about 74 to 75 percent of the total volume, i.e. a volume greater than is geometrically possible for close packing of mono-dispersed spheres.
HIPE'S possess radically different properties from emulsions of the low or medium internal phase ratio types. Specifically HIPE'S are non-Newtonian in nature exhibiting a yield valve phenomenon and a decrease in the effective viscosity with shear rate. In contrast to gels which require significant time periods to recover their body when subject to shear HIPE'S, or as they are also known, high internal phase ratio emulsions, recover to high viscosities almost instantaneously. Because of these radically different properties HIPE'S have been subject to investigation with respect to applications in such varied disciplines as: fuels, oil exploration, agricultural sprays, textile printing, foods, household and industrial cleaning, cosmetics, transport of solids, fire extinguishers, and crowd control to name just a few.
HIPE'S appear to have attracted very little interest prior to the mid-nineteen-sixties when workers in the fields of agricultural sprays, low flammability aircraft fuels and textile printing pastes, published papers describing their use properties and preparation. Representative of these early applications and etc. are set forth in the following publications which are incorporated herein by reference:
1. R. E. Ford, C. G. L. Furmidge, J. Colloid & Interface Sci., 22, 331-341 (1966). PA1 2. R. E. Ford, C. G. L. Furmidge, J. Sci. Food Agric., 18 (9), 419-28 (1967). PA1 3. J. P. Colthurst, C. G. L. Furmidge, R. E. Ford, J. A. Pearson. The Formulation of Pesticides. S. C. I. Monograph No. 21 (1966). PA1 4. J. Nixon, A. Beerbower, Am Chem. Soc. Petrochem. Preprints 14, 49-59 (1969). PA1 5. A. Beerbower, J. Nixon, Am. Chem. Soc. Petrochem. Preprints 14, 62-71 (1969). PA1 6. A. Beerbower, J. Nixon, W. Philippoff, T. J. Wallace, S. A. E. Transactions, Section 2, 1446-54 (1968). PA1 7. A. Beerbower, J. Nixon, T. J. Wallace, J. Aircraft, 5 (4), 367-72 (1968). PA1 8. J. Nixon, A. Beerbower, T. J. Wallace, Mech. Eng., 90 27-33 (1968). PA1 9. I. Rusgnak, L. G. Bercsenyi, Magy. Kem. Labja., 25 (9), 452-7 (1970). PA1 10. L. G. Berscenyi, Textilveredlung, 7 (12) 778-780 (1972). PA1 11. L. G. Berscenyi, M. I. Khalil, A. Kantouch, A. Hebeish, Kolor. Ertesito, 15, 254-260 (1973). PA1 12. L. G. Berscenyi, A. Hebeish, A. Kantouch, M. I. Khalil, Kolor. Ertesito, 16, 73-81 (1974). PA1 13. A. Kantouch, M. I. Khalil, L. G. Berscenyi, A. Hebeish, Kolor, Ertesito, 16, 140-147 (1974). PA1 1. K. J. Lissant, J. Colloid & Interface Sci., 22, 462-468 (1966). PA1 2. K. J. Lissant, J. Soc. Cosmetic Chem., 21, 141-154 (1970). PA1 3. K. J. Lissant, K. G. Mayhan, J. Colloid & Interface Sci., 42, 201-207 (1973). PA1 4. K. J. Lissant, Emulsions and Emulsion Technology. Part 1 (Dekka), 49-66 (1974). PA1 5. K. J. Lissant, B. W. Peace, S. H. Wu, K. G. Mayhan, J. Colloid & Interface Sci., 47, 416-423 (1974). PA1 6. K. J. Lissant, Colloid & Interface Sci., Proceedings of 50th Int. Conf., 4 473-485 (1976). PA1 7. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,343,599, Sept. 26, 1967. PA1 8. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,352,109, Nov. 14, 1967. PA1 9. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,396,537, Aug. 13, 1968. PA1 10. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,490,237, Jan. 20, 1970. PA1 11. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,523,826, Aug. 11, 1970. PA1 12. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,539,406, Nov. 10, 1970. PA1 13. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,565,817, Feb. 23, 1971. PA1 14. K. J. Lissant (Petrolite Corp.) U.S. Pat. No. 3,613,372, Oct. 19, 1971. PA1 15. K. J. Lissant (Petrolite Corps.), U.S. Pat. No. 3,617,095, Nov. 2, 1971. PA1 16. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,700,594, Oct. 24, 1972. PA1 17. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,732,166, May 8, 1973. PA1 18. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,974,116. Aug. 10, 1976. PA1 19. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,983,213, Sept. 28, 1976. PA1 20. K. J. Lissant (Petrolite Corp.), U.S. Pat. No. 3,988,508, Oct. 26, 1976. PA1 21. K. J. Lissant (Petrolite Corp.), G. B. Pat. No. 1227 345, Apr. 7, 1971. PA1 22. K. J. Lissant (Petrolite Corp.), G. B. Pat. No. 1227 346, Apr. 7, 1971. PA1 23. K. J. Lissant (Petrolite Corp.), G. B. Pat. No. 1465 528, Feb. 23, 1977. PA1 24. K. J. Lissant (Petrolite Corp.) G. B. Pat. No. 146 529, Feb. 23, 1977. PA1 25. K. J. Lissant (Petrolite Corp.), G. B. Pat. No. 146 530, Feb. 23, 1977. PA1 26. K. J. Lissant (Petrolite Corp.), Ger. Offen. 2408663, Aug. 7, 1975. PA1 1. is only sparingly soluble in water; PA1 2. has a low surface tension; and PA1 3. possesses a characteristic of a greasy feel to the touch. PA1 1. in cosmetics and drugs as an inexpensive vehicle or suspending medium for other ingredients such as sunscreens, emollients, humectants, etc,; PA1 2. in foods such as in dietary products, dressings, and sauces. PA1 1. about 1 to about 5 parts by weight of the condensation product of an amine, selected from the group consisting of mono-and dialkyl, mono-and dialkanol amines, said alkyl and alkanol amines having from 1 to 8 carbon atoms in the alkyl and alkanol chains, alkyl polyamines selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine, and mixtures thereof, with about an equal molar amount of a fatty acid chosen from the group consisting of aliphatic monocarboxylic acids having from 8 to 22 carbon atoms in the aliphatic chain and reactive esters and halides thereof; PA1 2. about 1/3 to about 2 parts by weight of a long chain aliphatic monohydric alcohol having from 8 to 22 carbon atoms in the aliphatic chain; and PA1 3. about 0 to about 5 parts by weight of a coupling agent selected from the group consisting of aliphatic monohydric alcohols having from about 3 to about 5 carbon atoms in the aliphatic chain, water immiscible liquid chlorinated hydrocarbons, and low boiling liquid aliphatic and aromatic hydrocarbons having fat solubilizing properties and mixtures thereof. Again as can be seen, the destabilizing action of the electrolyte required a specific and complex emulsifier system. PA1 1. is only sparingly soluble in water; PA1 2. has a low surface tension; and PA1 3. possesses a characteristic greasy feel to the touch. PA1 (a) C.sub.10 to C.sub.12 isoparafines such as ISOPAR L PA1 (b) Squalane such as COSBIOL PA1 (c) Branched chain parafin oil such as VASELINE OIL PA1 (d) Petrolatum such as VASELINE PA1 (e) Ethyl hexylpalmitate such as Wickenol 155 PA1 (d) C.sub.16 to C.sub.18 fatty alcohol di-isooctanoate such as CETIOL SN PA1 (f) Mineral oil such as that manufactured by ESSO PA1 (g) Polyisobutene such as PARLEAM PA1 1. accelerated room temperature aging via periodic centrifugation; PA1 2. storage at 125.degree. F.; and PA1 3. freeze-thaw (0.degree. to 70.degree.) cyclic storage, most, if not all, showed signs of deterioration of the emulsion. PA1 1. inorganic electrolytes; PA1 2. organic electrolytes; PA1 3. complex polyelectrolytes; and PA1 4. mixtures thereof. PA1 1. monovalent inorganic salts; PA1 2. divalent inorganic salts; PA1 3. trivalent inorganic salts; and PA1 4. mixtures thereof. PA1 1. salts of carboxylic acids; PA1 2. salts of amino acids; PA1 3. salts of organic phosphoric acids; PA1 4. salts of organic phosphonic acids; PA1 5. quaternary ammonium halides; PA1 6. quaternary ammonium acetates; and PA1 7. mixtures thereof. PA1 1. sodium pyrollidone carboxylate PA1 2. sodium lactate PA1 3. lactic acid PA1 4. triethanolamine lactate PA1 5. orotic acid PA1 6. inositol PA1 7. sodium chloride PA1 8. -hydroxy C.sub.6 to C.sub.10 carboxylic acids PA1 1. p-amino benzoic acid PA1 2. propoxylated (2)ethyl p-amino benzoate PA1 3. 2-hydroxy-4-n-octoxybenzophenone PA1 4. dipropylene glycol salicylate PA1 5. 2,2',4,4'-tetrahydroxybenzophenone PA1 6. 2-hydroxy-4-methoxy benzophone-5-sulphonic acid PA1 7. ethylexyl-2-cyano-3,3-diphenyl acrylate PA1 1. 2-bromo-2-nitro propan-1,3-diol PA1 2. cetyl pyridinium chloride PA1 3. 3,4,4'-trichlorocarbanilide PA1 4. 2,4,4'-trichloro-2'-hydroxydiphenyl ether PA1 5. benzalkonium chloride PA1 6. para-hydroxy benzoic acid PA1 7. dehydroacetic acid PA1 1. 2-ethyl-1,3-hexane diol PA1 2. 2,4,4' trichloro-2'-hydroxydiphenyl ether PA1 3. zinc oxide PA1 4. zinc phenylsulfonate PA1 1. aluminium chlorhydrate PA1 2. aluminium chloride PA1 3. sodium aluminium chlorhydroxy lactate complex PA1 4. zirconyl chlorhydrate
Recognized, perhaps, as one of the foremost workers in the areas of HIPE'S is K. J. Lissant of the Petrolite Corporation, St. Louis, Mo., who has published numerous papers in the field and who holds numerous patents related to HIPE technology. These publications and patents include the following which are incorporated herein by reference:
As stated, this invention relates to high-internal-phase emulsions. More particularly, the invention relates to HIPE'S wherein the liquid/liquid immiscible dispersed systems are water and oil, i.e. having an aqueous phase and an oil phase. By oil phase is meant a material, solid or liquid, but preferably liquid at room temperature that broadly meets the following requirements:
Materials included under this definition include, for example, but in no way limited to: straight, branched or cyclic parafin compounds, vegetable oils, esters of fatty acids, or alcohols and silicon oils.
Both oil-in-water, hereafter referred to as o/w, and water-in-oil, hereafter referred to as w/o, HIPE'S are subject to the instant invention. By oil-in-water is meant that the oil phase is dispersed in the water phase and conversely, by water-in-oil is meant that the water phase is dispersed in the oil phase.
While HIPE'S are defined as emulsions whose internal phase comprises more than about 74 to 75 of the emulsion by volume, usually, the volume fraction of the internal phase in such emulsions is greater than 90 percent and frequently is about 95 percent with some being reported as high as 98 percent.
Both o/w and w/o HIPE's have several properties which make them potentially useful in a variety of applications. These emulsions are viscous fluids and have appreciable yield values. Because of their high viscosity and lower flammability compared to the separate internal oil phase, these emulsions have been proposed as rocket and jet fuels. Water-in-oil emulsions which are 90-96 percent aqueous phase can be prepared in forms ranging from a pourable fluid to a stiff gel. These emulsions can find application in several areas such as:
Although these emulsions are attractive in terms of cost versus performance (since they are mainly water), the problem until now, has concerned the type of emulsifier required to produce emulsions of adequate stability.
Because HIPE'S are so concentrated, there is great stress applied to the films separating the water droplets in the emulsion. Such stress is quite demanding on the emulsifier and up until now, rather unique and in many cases, rather complicated or sophisticated and expensive emulsifiers were required to obtain reasonably stable HIPE'S. Such emulsifiers have not been readily available and must be specially synthesized. Moreover, since it is generally recognized that an emulsifier which works well with one emulsion composition may not work well with another emulsion composition, the synthesis of a wide range of expensive exotic emulsifiers is currently required in order to stabilize the various types of compositions for which one may to employ HIPE'S.